Polyazo dyestuffs containing metal



Patented Mar. 26, 1940 2,19%357' UNITED STATES PATENT OFFICE 2,194,857 I POLYAZO DYESTUFFS coummmc METAL Hans Krzikalla and Walter Limbacher, Ludwigshafen-on-the-Rhine, Germany, assignors to General Aniline & Film Corporation, acorporation of Delaware N Drawing. Application February 18, 1938, Serial No. 191,178. In Germany March 19, ,1937

3 Claims. (01.260447) The present invention relates to polyazo dyewith acetic acid. The finished dyestufi' is salted stufis containing metal.

We have found that very valuable polyazo dyestufi's containing metal are obtained by treating with agents supplying trivalent metal di'sazo or polyazo dyestufiswhich contain at least two sulphonic acid groups and which have been prepared by coupling 1 molecular proportion of tetrazotized 4.4-diaminodiphenyl-3.3'-dicarboxylic acid or its substitution products with 2 molecular proportions of azo components of which at least one is a pyrazolone derivative.

Suitable azo components of the pyrazolone series for the preparation of the dyestuffs are,

out, filtered oil by suction and washed. It is then dissolved in from about 500 to 600 parts of Water and heated for 3 hoursat 1 0 C. under, pressure with a chromium formate solution correspending to a content 01 18.4 parts of CrzOa.

The dyestufi' obtained, containing chromium, is

salted out, filtered off by suction and dried. It

dyes leather uniform red-orange shades of very good fastness to light, washing, acid and alkali. The nickel or cobalt compound prepared in a corresponding manner has similar properties.

Similar dyestufis are obtained by using 1-(3- sulphophenyl) S-methyl 5 pyrazolone, 1-(6'- for example, 1-(4'-sulpho-pheny1) -3-methyl-5- chlor-2-methyl-4-sulphophenyl) -3-methyl-5- w; pyrazolone, 1-(3'-sulphopheny1)-3-methyl-5-pypyrazolone or 1-(2'-ch1or-5-su1phophenyl)-3- razolone, 1-beta'-naphthyl-3-methyl-5-pyrazomethyl-5-pyrazolone as azo components. 1one-5'.'7-disulphonic acid, 1-beta'-naphthyl-3- Example 2 methyl-5-pyrazolone-4'.8'-disulph0nic acid, 1-

(2'-chlQI-5'-sulphopheny1)-3 -methy1-5-@yr3,zo- A tetrazo solution prepared from 27.2 parts lone, 1-phenyl-3-methy1 5- 1 or 3- of 4.4-diaminodiphenyl-3.3'-dicarboxylic acid is methyl-Ei-pyrazolone, If t dyestufi is prepared coupled with a solution of 84.4 parts of 1-beta'- while using only 1 molecular proportion of a pyy y -Dyr z0l0ne-4'.8-disulphonrazolone component, it is preferable t u as in acid in a solution rendered alkaline with soda. the other azo component compounds which hear, The resulting dyestufi is Worked in the in ortho-positign t t position in which the ner described in Example 1 and then chromed. coupling takes place, a group capable of forming The dyestufi containing chromium, dyes leather a metal complex, as, for example, naphtholsulred shades very fast to light, washing, acid and phonic acids or aminonaphthol-sulphonic acids, alkali such as 2.5-aminonaphthol hsulphonic acid, If y -Dy 0ne- 30 1.8-aminonaphthol -3.6-disulphonic acid, 2.8-amacid be used as 320 component, inonaphthol g s disulphonic acid or 1 a dyestuff having similar properties is obtained. aminonaphthol-3.6disulphonic acid as well as Emmple 3 the monoazo dyestufis obtainable by coupling cliazo compounds with 1.8-aminonaphthol-3.6-die 8911mm pr 3 from 1 paflrts I 35 sulphonic acid in acid solution. For the prep- 'dlamltlodlphenylfs's 'dmarboxyhc acld 1s araticn of the complex trivalent metal compounds ,Coupled Wlth sotutlon 3 there are employed mainly compounds of chro monaphthol-3.i5d1sulphon1c ac d which has been mium iron nickel or cobalt rendered alkaline with soda. The monoazo dyei The azo dyestufis containing trivalent metal i thus obtamfad .converted into the fiisazo 40 thus prepared are especially Suitable for dyeing dyestufiby reaction wlth an aqueous solut1on of animal fibers, especially leather of all kinds. parts of 'sulphopheriyl) They yield uniform dyeings which have Very pyrazolone. The dream dyestuff 1s salted out and good fastness to light, washing, acid and alkali. filtered Ofi and then chromed m the The following examples will further illustrate F descnbed.m Example The dyestufl- 1 how our said invention may be carried out in contammg chrommm" dyes leather fast brown practice, but the invention is not restricted to shades these examples. The parts are by weight. dyesmfi gwmg w more yellowlsh dyeings is obtained by using 1.8-acetylamino- E$ample 1 naphthol-3.6-disulphonic acid as azo component 50 A tetrazo solution prepared in the usual maninstead of 2.8-aminonaphthol-3.G-disulphonic ner from 27.2 parts of 4.4-diaminodiphenylacid. 3.3 dicarboxylic acid is coupled with a solution The dyeing of leather with the above menof 55.8 parts of LOP-sulphophenyl)-3-methyl-5- tioned dyestufis may be carried out in the folpyrazolone rendered alkaline with soda or acid lowing manner 5 Neutralized chrome leather is dyed in a. dyebath with a bath ratio of 1:4, which contains from 1 to 3 per cent of a complex metal compound of an azo dyestuff, for about to minutes at from to C. After adding about 2 per cent of sulphonated neats foot oil, the leather is dyed for a further 15 minutes, then 1 t0 3 per cent of acetic acid are added and dyeing m is continued for further 15 minutes. The leather is then rinsed and worked up in the usual manner.

Glac leather, which has been pretreated in the usual manner, may be dyed for 2 hours at 15 from 40 to 50 C. in a dye-bath with a bath ratio of 1:5 with from 1 to 3 per cent of the complex chromium compound of am azo dyestuff. A suspension of egg-yolk in water is then added, dyeing is continued for 30 minutes, from 0.5 to

20 1.5 per cent of formic acid per cent) and 1 per cent of chromium acetate being added after each 30 minutes. The leather thus dyed is rinsed and worked up as usual. (The bath ratio and the percentages are with respect to the weight of the leather).

What we claim is:

1. Complex trivalent metal compounds of polyazo dyestuffs of the general formula A1N=N-BN=NAz wherein A1 and A1 represent radicles of sulphonic acids of the pyrazolone series, and wherein B stands for a diphenyl dicarboxylic acid bearing the carboxyl groups in ortho-position to the azo groups.

2. Complex trivalent metal compounds of polyazo dyestuffs of the general formula HOOC COOK wherein A1 and A2 represent radicles of sulphonic acids of the pyrazolone series.

3. Complex trivalent metal compounds of polyazo dyestuffs of the general formula A1N=N N=N-A,

wherein A1 and A2 represent radicles of l-(sulphoaryl) -3-methyl-5pyrazolones.

HANS KRZIKALLA. WALTER LIMBACI-IER. 

